Water swellable and water soluble polymers and use thereof

ABSTRACT

The present invention provides a polymer comprising units according to formula III 
     
       
         
         
             
             
         
       
     
     wherein
 
R 1  is selected from C 1  to C 10  alkylene and C 5  to C 20  arylene; each R 2  is selected independently from H and C 1  to C 10  alkyl; and R 3  and R 4  are selected independently from H and C 1  to C 30  alkyl. Embodiments of the invention provide polymers that are water soluble or water swellable and can form transparent and flexible films.

REFERENCE TO RELATED APPLICATION

This application is a continuation of International Application No.PCT/SG2008/000218, filed Jun. 20, 2008, which is hereby incorporated byreference.

FIELD OF THE INVENTION

The present invention is concerned with water swellable and watersoluble polymers. In particular, water soluble polymers derived frompoly(maleic anhydride) and their use in wall coatings and water basedadhesives.

BACKGROUND

Water soluble and water swelling polymers have many applications.

Water soluble polymers are useful for making elastic coatings astemporary coverings for various surfaces like glass, metal and plastic.They can protect against mechanical damage and environmental degradationduring storage and transportation. Owing to their water soluble nature,dispersions free of solvents can be made in water and applied on thesesurfaces by spraying, rolling or dipping. The continuous film thusformed can be stripped off from the respective surface after storage andtransportation.

Water soluble polymers also can induce flocculation and thickeningproperties. Hence they are useful in water purification in variousindustries. Water swelling polymers are useful for making water basedgels which have applications in cosmetics and medicine.

Water soluble polymers are prepared by various methods. U.S. Pat. No.7,230,061 discloses the preparation of (meth)acrylic acid based watersoluble polymers with a high intrinsic viscosity. U.S. Pat. No.7,214,737 discloses the preparation of aqueous polymer dispersion ofacrylic or acrylic styrene with a high binding power towards fillers.U.S. RE39450 E discloses a water soluble polyvinyl pyridinium derivativeuseful as anti-dye transfer and colour protection agent. U.S. Pat. No.7,008,618 discloses a water soluble polymeric composition suitable forabsorbing UV radiation. U.S. Pat. No. 7,005,143 discloses water swellingpoly(alkylene oxide) based polymer gels. U.S. Pat. No. 6,472,136discloses a water soluble polymeric surfactant based on hydrolyzedmaleic anhydride derived co-polymers.

The anionic water soluble polymers that are commonly employed are:Poly(acrylic acid), acrylic or methacrylic acid derivatives such as thealkali metal and ammonium salts, polystyrene suphonate, carboxymethylcellulose, alginate salts etc. Polyethylene glycol is also watersoluble.

Polymers which swell in water are also termed as hydrogels. Hydrogelsare formed as a result of the absorption of water by super absorbentpolymers which are in general water insoluble due to crosslinking. Theyare capable of absorbing large amounts of aqueous liquids and bodyfluids such as urine and blood. Because of these characteristicabsorption properties these super absorbent polymers are mainly used insanitary articles such as diapers, sanitary napkins, and in thecultivation of plants etc. The following U.S. patents describe theformation and uses of super absorbent polymers: U.S. Pat. No. 7,173,086,U.S. Pat. No. 7,163,969, U.S. Pat. No. 7,163,966, U.S. Pat. No.6,087,450 and U.S. Pat. No. 6,087,450.

Commercially available super absorbent polymers are, mainly, crosslinkedpolyacrylic acids or crosslinked starch/acrylic acid graft co-polymerswherein the carboxyl groups are partially neutralized with sodium orpotassium ions. Indeed, known water soluble polymers are generallyprepared by neutralizing a polymer bearing carboxylic acids with alkalimetals.

SUMMARY AND DESCRIPTION OF PREFERRED EMBODIMENTS

The present inventors have noted that known water soluble polymers ofthe sort used to form temporary coverings are not able to form cleartransparent coatings. For example, a hazing or “crazing” can occur.

At its broadest, the present invention proposes that cyclic imidosulfonic acid groups should be incorporated into a polymer to providenovel and useful water swellable or water soluble polymers. Inparticular, the present inventor has found that such useful waterswellable or water soluble polymers can be made from poly(cyclicanhydride) by reaction with an amino sulfonic acid to form a polymerhaving repeating units comprising cyclic imido sulfonic acid.

Particularly useful examples of this include derivatives of poly(maleicanhydride), including copolymers of poly(maleic anhydride), which areformed by reaction of the poly(maleic anhydride) with alkyl or arylamino sulfonic acids.

Furthermore, quaternary ammonium salts of such polymers, suitably formedby addition of a tertiary amine, demonstrate surprising advantages withrespect to known water soluble or water swellable polymers.

In a first aspect, the present invention provides a polymer havingrepeating units comprising a cyclic imido sulfonic acid according toformula I

wherein X and Y are selected to form an optionally substituted cyclicimido; and R_(S) is a sulfonic acid-containing group or salt thereof.

Suitably X and Y are selected so that the cyclic imido is apyrrolidine-2,5-dione.

These polymers show better solubility in water than polyvinyl alcoholand also the corresponding alkali metal salts obtained by the hydrolysisof poly(maleic anhydride).

The solutions prepared by dissolving the polymer of the presentinvention in water are clear, transparent and less viscous whereas thesolutions obtained by dissolving polyvinyl alcohol and the metal saltsobtained by the hydrolysis of poly(maleic anhydride) are turbid.

Aqueous solutions of the polymer of the present invention can be used toform clear, transparent, uniform coatings on substrates like glass. Afree standing, flexible, transparent film can be obtained by casting apolymer solution of the present invention on a glass plate.

The polymer can be used as a component in a paint composition, where itcan significantly reduce the contact angle of the coating with water,thereby aiding the waterproofness of the paint composition. This canalso make it easier to clean the paint composition. This makes thepolymer particularly suitable for use in exterior paint compositions.

The polymer is preferably a free radical addition polymer. As discussedin more detail below, the polymer can be a homopolymer or a copolymer.

Suitably the cyclic imido sulfonic acid is formed by the reaction of acyclic anhydride with an amino sulfonic acid. The present inventor hasfound that a cyclic anhydride is particularly effective for forming thecyclic imido sulfonic acid in a simple one-step reaction. Suitably thereaction between the amine and the —O— moiety of the anhydride causesformation of the imido group. In preferred embodiments, the reactionproceeds as follows:

wherein R is a spacer, typically optionally substituted alkylene orarylene.

Suitably the cyclic anhydride precursor is present in the form ofpoly(cyclic anhydride). Thus, it is preferred that the starting materialis a polymer. In particular, it is preferred that the formation of thecyclic imido sulfonic acid occurs by selective reaction of a cyclicanhydride repeating unit in the starting material polymer.

The cyclic anhydride can be any cyclic anhydride, provided it has anethylenically unsaturated bond suitable for free radical polymerisation.In other words, the cyclic anhydride must be capable of polymerisationto form poly(cyclic anhydride). Preferred cyclic anhydrides includealicyclic or aromatic anhydrides.

In particularly preferred embodiments the cyclic anhydride is maleicanhydride. Thus, a preferred starting material is poly(maleicanhydride). The present invention is therefore concerned in preferredembodiments with a polymer comprising units derived from maleicanhydride. However, other cyclic anhydrides, and hence correspondingpoly(cyclic anhydrides), can be used.

It follows that the polymer units comprising imido sulfonic acid formedfrom the poly(cyclic anhydride) will have a cyclic imido structurecorresponding to the cyclic structure of the anhydride. For example,cyclic imido structures comprising succinimidyl or phthalimidyl arepreferred.

The water soluble or water swellable properties of the polymer of thepresent invention are particularly surprising given that the preferredstarting polymer of poly(maleic anhydride) is insoluble in water.

Furthermore, the film forming properties of the polymer of the presentinvention are also surprising given that the preferred starting materialpoly(maleic anhydride) forms a brittle, non-continuous film upon castingand is non-transparent. Similarly, the hydrolyzed product of thepoly(maleic anhydride) when cast from aqueous solution on a glass plateresults in an unsatisfactory film, being non-uniform, non-transparentand inhomogeneous.

Surprisingly, the present inventor has found that the advantageousproperties of the polymer of the present invention can be obtainedindependently of the exact structure of the cyclic imido sulfonic acid.Thus, provided the polymer has repeating units comprising the cyclicimido sulfonic acid, the polymer will suitably exhibit at least some ofthe properties described herein.

The cyclic imido group may be important for its ability to introducerigidity and hence planarity to the repeating units of the polymer.

The provision of a sulfonic acid or sulfonic acid salt-containing groupas the imido substituent imparts the polymer with a strong interactionwith water and also with nitrogen-containing organic. In particular, byproviding an interaction that favours the inclusion of a tertiary aminebase (examples of which are discussed below) an ionic interaction can beachieved between polymer chains. Indeed, long range interchaininteraction is believed to assist in the formation of films, and is adesirable property of polymers of the present invention. In addition,the provision of these groups contributes to the excellent watersolubility or water swellability of the polymer.

Furthermore, the ionic nature of the polymer leads to long rangeinteraction between polymer chains. Due to this increased interaction,the chains can align together which assists in film formation.

Preferably the amino sulfonic acid is NH₂—R₁—SO₃H, wherein R₁ isselected from optionally substituted C₁ to C₁₀ alkylene and C₅ to C₂₀arylene. The amino group reacts with the anhydride functionality toproduce the desired imido group. The present inventor has found thatthis reaction can be used to reliably convert an anhydride to an imidoeven when the anhydride is part of a polymer.

Thus, a particular advantage of using an amino sulfonic acid is that thereaction to form the polymer can be carried out in a single step, i.e. a“one pot” reaction. Thus, starting from a poly(cyclic anhydride), thepolymer can be formed in a single step, by addition of the aminosulfonic acid to the poly(cyclic anhydride).

Particularly preferred amino sulfonic acids are taurine(2-aminoethanesulfonic acid) and metanilic acid (3-aminobenzenesulfonicacid). Taurine is most preferred.

The present inventor has found that the polymer exhibits particularlyuseful properties, particularly in respect of film formation, when thesulfonic acid is present as a salt. Thus, R_(S) in formula I is suitablya sulfonic acid salt. Particularly preferred salts are quaternaryammonium salts and alkali metal salts. Quaternary ammonium salts producethe best results and are therefore most preferred. Its ambiphilic natureenables the polymer to be soluble or swellable in water whilstpreferably also being soluble in organic solvents.

If alkali metal salts are used, monovalent counterions such as lithiumand sodium are preferred. Divalent counterions such as calcium andmagnesium can also be used, as can multivalent counterions but these areless preferred because they may lead to the formation of a crosslinkedpolymer. Nevertheless, divalent and multivalent counterions may be usedwhere flocculation is desired.

Suitably, in addition to the units comprising imido sulfonic acid groupsaccording to formula I, the polymer comprises units derived from atleast one ethylenically unsaturated monomer. Thus, suitably, the polymeris a copolymer. It can be selected from periodic copolymers, randomcopolymers, statistical copolymers and block copolymers. An alternatingcopolymer is preferred.

The ethylenically unsaturated monomer(s) can be selected from any of theknown types of free radical polymerisable monomers often used ascomonomers. Indeed, by selecting an appropriate comonomer or comonomersit is possible to adjust the interaction of the polymer with water andthereby control the behaviour of the polymer when mixed with water. Forexample, the polymer could be adjusted by appropriate choice ofcomonomer(s) so that it dissolves readily in water, swells beforedissolving or remains swollen without dissolving.

Particularly preferred ethylenically unsaturated monomers are alkenes(e.g. ethylene, propylene, octadecene), styrene, vinyl pyrrolidine,(meth)acrylate(s) (in particular, methyl methacrylate), isobutene, vinylpyridine, acrylonitrile, vinyl chloride and acrylic acid. An additionalbenefit of these, and other ethylenically unsaturated monomers, is thatthey copolymerise readily with the preferred monomer maleic anhydride.

As used herein, the term “(meth)acrylate(s)” includes acrylate(s) andmethacrylate(s), as is well known in the art. Similarly, the term“(meth)acrylic acid” includes acrylic acid and methacrylic acid, as iswell known in the art.

The units derived from these comonomers are suitably present, as a % oftotal units of comonomer and units comprising cyclic imido sulfonicacid, in an amount of up to about 50%, preferably up to 40%, morepreferably up to 30%.

Suitably the polymer consists essentially of units according to formulaeI and units derived from at least one ethylenically unsaturated monomer.

Thus, preferably the polymer comprises

(1) 50 to 100% units according to formula II

wherein R₁ is selected from optionally substituted C₁ to C₁₀ alkyleneand C₅ to C₂₀ arylene, or a salt thereof; and(2) 0 to 50% units derived from at least one ethylenically unsaturatedmonomer.

In this way, the properties of the polymer can be tuned, byincorporation of appropriate amounts of the ethylenically unsaturatedmonomer.

Whilst the above structure (and those given below) represent analternating copolymer, the present invention also includes, as discussedabove, other copolymer arrangements, such as periodic copolymers, randomcopolymers, statistical copolymers and block copolymers. For each ofthese other copolymers, the optional and preferred features describedherein also apply.

In particularly preferred embodiments, the polymer comprises unitsaccording to formula III

whereinR₁ is selected from optionally substituted C₁₀ to C₁₀ alkylene and C₅ toC₂₀ arylene;each R₂ is selected independently from H and optionally substituted C₁to C₁₀ alkyl; andR₃ and R₄ are selected independently from H and optionally substitutedC₁ to C₃₀ alkyl, C₅ to C₂₀ aryl, pyrrolidinyl, carboxy and ester.

Preferably R₃ and R₄ are selected independently from H and optionallysubstituted C₁ to C₂₀ alkyl, more preferably from H and optionallysubstituted C₁₀ to C₂₀ alkyl, more preferably from H and optionallysubstituted C₁₅ to C₁₈ alkyl, and most preferably from H and optionallysubstituted C₁₅ to C₁₈ alkyl.

Preferably R₃ and R₄ are unsubstituted.

In particularly preferred embodiments, R₃ is H and R₄ is hexadecyl.

In other embodiments, R₃ and R₄ are selected independently from H andoptionally substituted C₅ to C₂₀ aryl, preferably from H and optionallysubstituted phenyl.

In yet further embodiments, R₃ and R₄ are selected independently from Hand optionally substituted carboxy and ester, preferably ester, whereinthe ester is preferably —C(═O)OCH₃.

Suitably R₁ is selected from optionally substituted C₁ to C₆ alkyleneand C₅ to C₁₅ arylene, preferably from optionally substituted C₁ to C₄alkylene and C₅ to C₁₀ arylene, and more preferably from optionallysubstituted C₂ to C₄ alkylene and C₅ to C₈ arylene.

Suitably R₂ is unsubstituted.

In particularly preferred embodiments, R₁ is selected from ethylene andphenylene.

Suitably each R₂ is selected independently from H and optionallysubstituted C₁ to C₁₀ alkyl, preferably from H and optionallysubstituted C₁ to C₆ alkyl, more preferably from H and optionallysubstituted C₁ to C₃ alkyl.

Suitably R₂ is unsubstituted.

In particularly preferred embodiments, each R₂ is selected independentlyfrom H and ethyl. Even more preferably, each R₂ is ethyl.

In particularly preferred embodiments, the polymer has a structureaccording to formula IIIa

wherein each of R₁, R₃ and R₄ are as discussed above.

The present inventor has found that the properties of the polymer can befurther enhanced and/or controlled if, in addition to the unitscomprising cyclic imido sulfonic acid, the polymer includes unitscomprising cyclic imido having a pendant group bonded to the imidonitrogen, wherein the pendant group is other than a sulfonic acid.Preferably the pendant group is a neutral species (non-ionic),preferably an optionally substituted alkyl or aryl.

Suitably the pendant group is formed by reacting a grafting componentwith the cyclic anhydride units of the poly(cyclic anhydride) precursor.More specifically, those cyclic anhydride units that are not reacted,e.g. with amino sulfonic acid, so as to form sulfonic acid-containinggroups (R_(S) above) can then be reacted with an appropriate graftingcomponent. Suitable grafting components comprise a primary amine groupto facilitate reaction with the anhydride.

Indeed, the polymer demonstrates considerable flexibility in terms ofits solubility or extent of swelling in water. These properties can bemodified to adjust the polymer from water soluble to water swelling bychanging the grafting components, and hence pendant groups on the imidounits. This is surprising because conventionally water solubility andswellability can only be adjusted significantly by subjecting a watersoluble polymer to undergo crosslinking.

The grafting component can be selected so as to provide a pendant groupselected from alkyl, hydroxyl substituted alkyl or amine substitutedalkyl. However, the grafting component can also be an aliphatic oraromatic amino acid.

Thus, in addition to units according to formula III, the polymerpreferably also comprises units according to formula IV

wherein R₅ is selected from optionally substituted C₁ to C₁₀ alkyl andC₅ to C₂₀ aryl; andR₃ and R₄ are as defined above.

Preferably R₅ is selected from optionally substituted C₂ to C₈ alkyl,more preferably selected from amine and hydroxyl substituted C₂ to C₈alkyl.

Suitably R₅ is optionally substituted C₆ alkyl. Preferably it isselected from hexyl and hexamethylamine.

It is also preferred that R₅ is optionally substituted C₂ alkyl,preferably ethylalcohol.

It is particularly preferred that R₅ is selected from hexyl,hexamethylamine and ethylalcohol.

Suitably the polymer consists essentially of units according to formulaeIII and IV.

Suitably the polymer includes more than one type of pendant group, suchthat there are two or more types of repeating units that comprise thereaction product of a cyclic anhydride and a grafting component. In thisway, further control of the polymer's properties can be achieved.

Accordingly, it is preferred that the polymer comprises units accordingto formulae III, IV and V

whereinR₁ is as defined above;each R₃ and R₄ is independently as defined above; andR₅ and R₆ are selected independently from the definitions of R₅ givenabove.

Suitably R₅ and R₆ are different.

It is preferred that the units according to formula III are present, asa % of all of the units, in an amount of at least 50%. Thus, suitably,the ratio of units of formula III to the total number of units offormulae IV and V is at least 1. Preferably the ratio is at least 5,more preferably at least 10. Suitably the polymer consists essentiallyof units according to formulae III, IV and V.

The present inventor has found that the water swellable properties ofthe polymer can be further controlled by introducing crosslinking intothe polymer. For example, this can be achieved by providing a pendantgroup on some of the cyclic imido units, which pendant group carries agroup capable of reacting with a cyclic anhydride group on another partof the polymer. An example of such a group is a primary amine. Thus, asuitable pendant group would be an alkyl amine. Indeed, as noted above,one of the preferred R₅ and R₆ substitutents is hexamethylamine, whichcan be provided by the grafting component hexamethylenediamine, byreaction with a cyclic anhydride.

Thus, suitably the polymer is crosslinked.

Preferably the polymer comprises crosslinking groups according toformula VI

wherein R₇ is selected from optionally substituted C₁ to C₁₀ alkyleneand C₅ to C₂₀ arylene. Optionally substituted C₁ to C₁₀ alkylene ispreferred, with optionally substituted C₃ to C₈ alkylene andparticularly C₆ alkylene being especially preferred.

Whilst an appropriate degree of crosslinking can be selected in order toprovide the polymer with a desired level of water swellability, it ispreferred that the degree of crosslinking, being the % of units that arecrosslinked, is no more than 50%. In particular, the degree ofcrosslinking has been found to help control the mechanical stability ofthe swollen polymer. With this in mind, the skilled reader will be ableto select an appropriate degree of crosslinking based on theapplication.

Suitably the molecular weight of the polymer (as measured by gelpermeation chromatography with polystyrene standards) is in the range of1000 to 1,000,000, preferably in the range of 5000 to 500,000, and morepreferably in the range of 10,000 to 100,000.

Suitably the polymer is resistant to weight loss below 300° C. Weightloss measurements are made in the conventional way by thermogravimetricanalysis (TGA) under a nitrogen atmosphere with a heating rate of 10°C./min.

Preferably the polymer exhibits a weight loss at 300° C. of no more than10 wt %, preferably no more than 8 wt % and most preferably no more than6 wt %.

Preferably the polymer exhibits a weight loss at 336° C. of no more than20 wt %, preferably no more than 15 wt % and most preferably no morethan 12 wt %.

Preferably the polymer exhibits a weight loss at 358° C. of no more than30 wt %, preferably no more than 25 wt % and most preferably no morethan 22 wt %.

Preferably the polymer is water swellable. The % swelling in water iscalculated as follows:

swelling={([Weight of swollen polymer−weight of dry polymer]/weight ofdry polymer)×100}

The measurement is made with deionised water and the polymer is allowedto reach equilibrium swelling

Preferably the polymer exhibits a % swelling in water of at least 100%,more preferably at least 200% and most preferably at least 300%

Suitably, the polymer exhibits reversible swelling. Preferably afterfive cycles of swelling and drying at least 80% of the % swellingobserved in the first cycle is achieved, preferably at least 90%, andmore preferably at least 95%. Suitably, reversible swelling is achievedafter 10 cycles of swelling and drying. Drying is carried out at 80° C.for 24 hours.

Preferably the polymer is water soluble.

In a further aspect, the present invention provides a method of forminga polymer comprising the step of:

-   -   (1) reacting a poly(cyclic anhydride) with an amino sulfonic        acid to form poly(imido sulfonic acid).

Suitably the poly(cyclic anhydride) is a co-polymer comprising unitsderived from (i) maleic anhydride and (ii) at least one ethylenicallyunsaturated monomer. Suitably it is an alternating copolymer.

Preferably the co-polymer is selected from poly(maleicanhydride-alt-octadecene), poly(maleic anhydride-alt-α-olefin),poly(maleic anhydride-alt-1-tetradecene) and poly(maleicanhydride-alt-isobutene).

Suitably the amino sulfonic acid in step (1) is used in asub-stoichiometric amount such that not all of the cyclic anhydride isconverted to an imido sulfonic acid in step (1), and the method includesthe step of (2) reacting the poly(cyclic anhydride) with a primaryamine.

Preferably steps (1) and (2) occur simultaneously.

Preferably the method includes the further step of adding a tertiaryamine to the reaction product of step (1) or step (2) to form aquaternary ammonium salt.

Preferably tertiary amine is added at the start of, or shortly after,step (1). In other words it is preferred that the poly(cyclicanhydride), amino sulfonic acid and tertiary amine are reacted togethersimultaneously.

Suitably the reaction temperature of step (1) is in the range of roomtemperature to 200° C., preferably in the range 60° to 180° C. Theduration of heating is preferably at least 15 hours, more preferablyabout 18 hours.

Preferably the reaction occurs in a dipolar aprotic solvent. It is alsopreferred that the reaction occurs in a high boiling point polarsolvent. Suitably the boiling point of the solvent is higher than thatof water. Preferably it is at least 110° C.]

Preferably the solvent is selected from N,N-dimethyl formamide,N,N-dimethyl acetamide and N-methylpyrrolidone. N,N-dimethyl formamideis most preferred.

In preferred embodiments the reaction (e.g. the reaction between thepolymeric anhydride and the aminosulfonic acid in the presence oftriamine) is carried out in the absence of solvent. Thus, a furtheradvantage of the invention is the possibility of solvent-free reactionconditions.

In a particularly preferred embodiment of the present invention, thepolymer is prepared according to Scheme 1:

wherein each of R₁, R₃ and R₄ are as defined above.

This represents an efficient “one pot” synthesis of a quaternaryammonium salt of an imido sulfonic acid group-containing polymer.

As noted above, the most preferred amino sulfonic acids are taurine andmetanilic acid and so R₁ is preferably ethylene or phenylene.

In a further aspect, the present invention provides a polymer formed bythe method of the previous aspect.

In a further aspect, the present invention provides a latex comprising apolymer according to the present invention.

In a further aspect, the present invention provides a paint compositioncomprising a polymer according to the present invention.

Preferably the paint composition has a contact angle of less than 75°,more preferably less than 70° and most preferably less than 67°. Thecontact angle is measured with water by a static method using agoniometer. The measurement was made by providing the aqueous coatingsamples with the additive and without the additive and spreading themevenly on a microscopic glass slide and allowing to dry under ambientconditions. A drop of water was placed on the coated surface with thehelp of a syringe and viewed through a goniometer. The angle generatedwas measured by the goniometer controlled by a computer. Thus, thepolymer of the present invention can be used as a contact angle loweringadditive. By lowering the contact angle, the polymer makes the paintcomposition more hydrophilic, which results in better surfacewettability and ease of cleaning.

In a further aspect, the present invention provides an adhesivecomprising a polymer according to the present invention.

In a further aspect, the present invention provides a surfactantcomposition comprising a polymer according to the present invention.

Suitably the surfactant is a liquid. However, it can also be a solid.

In a further aspect, the present invention provides a method of making apolymer latex, the method comprising the step of dispersing the polymerof the present invention in water.

In a further aspect, the present invention provides a method ofpreparing a paint composition, the method comprising the step of mixingthe polymer of the present invention with water.

Suitably the method includes the step of adding a pigment.

In a further aspect, the present invention provides a method ofpreparing an adhesive, the method comprising the step of adding thepolymer of the present invention to water.

In a further aspect, the present invention provides a method ofpreparing a surfactant composition, the method comprising the step ofadding a polymer of the present invention to the composition.

In a further aspect, the present invention provides use of a polymeraccording to the present invention in a latex.

In a further aspect, the present invention provides use of a polymeraccording to the present invention in a paint composition.

In a further aspect, the present invention provides use of a polymeraccording to the present invention in a surfactant composition.

Chemical Terms

Alkylene: The term “alkylene,” as used herein, pertains to a bidentatemoiety obtained by removing two hydrogen atoms, either both from thesame carbon atom, or one from each of two different carbon atoms, of ahydrocarbon compound having from 1 to 20 carbon atoms (unless otherwisespecified), which may be aliphatic or alicyclic, and which may besaturated, partially unsaturated, or fully unsaturated. Thus, the term“alkylene” includes the sub-classes alkenylene, alkynylene,cycloalkylene, etc., discussed below.

Examples of linear saturated C₁ to C₇ alkylene groups include, but arenot limited to, —(CH₂)_(n)— where n is an integer from 1 to 7, forexample, —CH₂— (methylene), —CH₂CH₂— (ethylene), —CH₂CH₂CH₂—(propylene), and —CH₂CH₂CH₂CH₂— (butylene).

Examples of branched saturated C₁₋₇alkylene groups include, but are notlimited to, —CH(CH₃)—, —CH(CH₃)CH₂—, —CH(CH₃)CH₂CH₂—,—CH(CH₃)CH₂CH₂CH₂—, —CH₂CH(CH₃)CH₂—, —CH₂CH(CH₃)CH₂CH₂—, —CH(CH₂CH₃)—,—CH(CH₂CH₃)CH₂—, and —CH₂CH(CH₂CH₃)CH₂—.

Examples of linear partially unsaturated C₁ to C₇alkylene groupsinclude, but is not limited to, —CH═CH— (vinylene), —CH═CH—CH₂—,—CH₂—CH═CH₂—, —CH═CH—CH₂—CH₂—, —CH═CH—CH₂—CH₂—CH₂—, —CH═CH—CH═CH—,—CH═CH—CH═CH—CH₂—, —CH═CH—CH═CH—CH₂—CH₂—, —CH═CH—CH₂—CH═CH—, and—CH═CH—CH₂—CH₂—CH═CH—.

Examples of branched partially unsaturated C₁ to C₇alkylene groupsinclude, but is not limited to, —C(CH₃)═CH—, —C(CH₃)═CH—CH₂—, and—CH═CH—CH(CH₃)—.

Examples of alicyclic saturated C₁ to C₇alkylene groups include, but arenot limited to, cyclopentylene (e.g., cyclopent-1,3-ylene), andcyclohexylene (e.g., cyclohex-1,4-ylene).

Examples of alicyclic partially unsaturated C₁ to C₇alkylene groupsinclude, but are not limited to, cyclopentenylene (e.g.,4-cyclopenten-1,3-ylene), cyclohexenylene (e.g., 2-cyclohexen-1,4-ylene;3-cyclohexen-1,2-ylene; 2,5-cyclohexadien-1,4-ylene).

Arylene: The term “arylene,” as used herein, pertains to a bidentatemoiety obtained by removing two hydrogen atoms, one from each of twodifferent aromatic ring atoms of an aromatic compound, which moiety hasfrom 3 to 20 ring atoms (unless otherwise specified). Preferably, eachring has from 5 to 7 ring atoms.

The ring atoms may be all carbon atoms, as in “carboarylene groups”(e.g., C₅ to C₂₀ carboarylene).

Examples of C₅ to C₂₀ arylene groups which do not have ring heteroatoms(i.e., C₅ to C₂₀ carboarylene groups) include, but are not limited to,those derived from the compounds discussed above in regard to carboarylgroups.

Alternatively, the ring atoms may include one or more heteroatoms, as in“heteroarylene groups” (e.g., C₅ to C₂₀ heteroarylene).

Examples of C₅ to C₂₀ heteroarylene groups include, but are not limitedto, those derived from the compounds discussed above in regard toheteroaryl groups.

Arylene-alkylene: The term “arylene-alkylene,” as used herein, pertainsto a bidentate moiety comprising an arylene moiety, -Arylene-, linked toan alkylene moiety, -Alkylene-, that is, -Arylene-Alkylene-.

Examples of arylene-alkylene groups include, e.g., C₅ to C₂₀ arylene-C₁to C₇ alkylene, such as, for example, phenylene-methylene,phenylene-ethylene, phenylene-propylene, and phenylene-ethenylene (alsoknown as phenylene-vinylene).

Alkylene-arylene: The term “alkylene-arylene,” as used herein, pertainsto a bidentate moiety comprising an alkylene moiety, -Alkylene-, linkedto an arylene moiety, -Arylene-, that is, -Alkylene-Arylene-.

Examples of alkylene-arylene groups include, e.g., C₅ to C₂₀ alkylene-C₁to C₇ arylene, such as, for example, methylene-phenylene,ethylene-phenylene, propylene-phenylene, and ethenylene-phenylene (alsoknown as vinylene-phenylene).

Carboxy (carboxylic acid): —C(═O)OH.

Ester (carboxylate, carboxylic acid ester, oxycarbonyl): —C(═O)OR,wherein R is an ester substituent, for example, a C₁₋₇alkyl group, aC₃₋₂₀heterocyclyl group, or a C₅₋₂₀aryl group, preferably a C₁₋₇alkylgroup. Examples of ester groups include, but are not limited to,—C(═O)OCH₃, —C(═O)OCH₂CH₃, —C(═O)OC(CH₃)₃, and —C(═O)OPh.

Amino sulfonic acid: a molecule comprising both amine and sulfonic acid.Examples include N(R)₂—R₁—SO₃H wherein each R is H, an alkyl or an aryl,and R₁ is alkylene or arylene.

Sulfonic acid: —S(═O)₂—OH

The term “Cyclic” as used herein, pertains to a group which has at leastone ring.

Where a cyclic compound has two or more rings, they may be fused (e.g.,as in naphthalene, decalin, etc.), bridged (e.g., as in norbornane,adamantane, etc.), spiro (e.g., as in spiro[3.3]heptane), or acombination thereof. Cyclic groups with one ring may be referred to as“monocyclic” or “mononuclear,” whereas cyclic groups with two or morerings may be referred to as “polycyclic” or “polynuclear.”

The term “unsaturated,” as used herein, pertains to compounds and/orgroups which have at least one carbon-carbon double bond orcarbon-carbon triple bond. Compounds and/or groups may be partiallyunsaturated or fully unsaturated.

Substituents

The phrase “optionally substituted,” as used herein, pertains to a groupwhich may be unsubstituted or which may be substituted.

Unless otherwise specified, the term “substituted,” as used herein,pertains to a group which bears one or more substitutents. The term“substituent” is used herein in the conventional sense and refers to achemical moiety which is covalently attached to, or if appropriate,fused to, a parent group. A wide variety of substituents are well known,and methods for their formation and introduction into a variety ofparent groups are also well known.

Examples of substituents include those listed above under the heading“definitions”. Typical substituents are:

—F, —Cl, —Br, and —I; —OH; —OMe, —OEt, —O(tBu), and —OCH₂Ph; —SH; —SMe,—SEt, —S(tBu), and —SCH₂Ph; —C(═O)H; —C(═O)Me, —C(═O)Et, —C(═O)(tBu),and —C(═O)Ph; —C(═O)OH; —C(═O)OMe, —C(═O)OEt, and —C(═O)O(tBu);—C(═O)NH₂, —C(═O)NHMe, —C(═O)NMe₂, and —C(═O)NHEt;

—NHC(═O)Me, —NHC(═O)Et, —NHC(═O)Ph, succinimidyl, and maleimidyl;

—NH₂, —NHMe, —NHEt, —NH(iPr), —NH(nPr), —NMe₂, —NEt₂, —N(iPr)₂,—N(nPr)₂, —N(nBu)₂, and —N(tBu)₂; —CN; —NO₂;

-Me, -Et, -nPr, -iPr, -nBu, -tBu;—CF₃, —CHF₂, —CH₂F, —CCl₃, —CBr₃, —CH₂CH₂F, —CH₂CHF₂, and —CH₂CF₃;—OCF₃, —OCHF₂, —OCH₂F, —OCCl₃, —OCBr₃, —OCH₂CH₂F, —OCH₂CHF₂, and—OCH₂CF₃;

—CH₂OH, —CH₂CH₂OH, and —CH(OH)CH₂OH; —CH₂NH₂, —CH₂CH₂NH₂, and—CH₂CH₂NMe₂; and

phenyl.

Any one or more of the aspects of the present invention may be combinedwith any one or more of the other aspects of the present invention.Similarly, any one or more of the features and optional features of anyof the aspects may be applied to any one of the other aspects. Thus, thediscussion herein of optional and preferred features may apply to someor all of the aspects. In particular, optional and preferred featuresrelating to the nature of the polymer apply to all of the aspects.Furthermore, optional and preferred features associated with a method oruse may also apply to a product, and vice versa.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the IR spectrum of the polymer of Example 1;

FIG. 2 shows the TGA curve of the polymer of Example 1; and

FIG. 3 shows the swelling curve of the polymer of Example 1

EXAMPLES Example 1 Preparation of Quaternary Ammonium Salt of SulfonicAcid Group Containing Polymer

To an oven dried single neck round bottom flask, poly(maleicanhydride-alt-octadecene) (10 g), and taurine (3.57 g) were added. Thesetwo solids were stirred slowly using a magnetic stirrer. DryN,N-dimethylformamide (DMF) (100 mL) was added through a syringe and thestirrer speed was increased. Triethylamine (2.89 g, 4 mL) was thenadded. The suspension turned light brown immediately after the additionof tertiary amine. The flask was then fitted with a double surfacecondenser and a drying tube on top of the condenser. This reactionmixture was heated in an oil bath at 160° C. for 18 h.

The reaction flask was then cooled and the DMF solution was addeddropwise to a beaker containing a large excess of ethyl acetate andstirred well. The solid separated was allowed to settle. Theethylacetate layer was decanted off and the solid residue was washedrepeatedly with ethyl acetate. Then the beaker was air dried to constantweight.

Yield 13 g. Gel Permeation Chromatography (Polystyrene standard; THFeluent): Mn=10563; Mw=16924; Polydispersity=1.60.

IR (KBr) cm⁻¹: 3449, 2924, 2853, 2759, 2739, 2679, 2492, 1772, 1699,1468, 1447, 1405, 1365, 1348, 1192, 1044, 737, 668. The IR spectrum (1)is shown in FIG. 1. Spectrum (2) is that of the starting material, viz.poly(maleic anhydride-alt-octadecene). The labelled peaks for spectrum(2) are the asymmetric and symmetric stretching of anhydride carbonyls,1856 and 1779 cm⁻¹ respectively. In spectrum (1), the labelled peaks aredue to the asymmetric and symmetric stretching of imide carbonyls, 1772and 1699 cm⁻¹ respectively.

¹H-NMR (CDCl₃) δ(ppm): 0.8-0.9 (t), 1.1-1.3 (b), 1.3-1.4 (t), 2.7-2.8(b), 3-3.1 (b), 3.13.3 (b), 3.6-3.8 (b), 9.5-9.8 (b). ¹³C-NMR (CDCl₃)δ(ppm): 8.75, 14.1, 22.5, 27.77, 29.37, 29.76, 31.92, 34.73, 35.42,38.75, 47.43, 49.38, 50.1, 179.1.

The observed ¹³C-NMR values correlated well with theoretical valuescalculated using ChemDraw® for the structure

Thermogravimetric analysis (TGA) (Nitrogen atmosphere; heating rate: 10°C./min): 5% weight loss at 298° C., 10% weight loss at 336° C. and 20%weight loss at 358° C. The weight loss curve (1) is shown in FIG. 2, andshows weight loss in mg (Y axis) obtained directly from the TGAinstrument.

The contribution of triethyl amine (TEA) to the polymer is 18.1 wt %.Assuming that the TEA is not strongly bound to the polymer, it would beexpected to observe a higher weight loss at lower temperatures due tothe low boiling point of TEA (bp 88.8° C.). However, this was notobserved, indicating that the TEA is strongly bound to the polymer anddoes not leave the polymer chain until the degradation of the backbonebegins to occur. The thermogram that is marked as 2 in FIG. 2 is that ofthe starting material, viz. poly(maleic an hydride-alt-octadecene).

The contribution of triethyl amine (TEA) in terms of weight % to thepolymer can be calculated by using the equation:

$\begin{matrix}{{{WT}\mspace{14mu} \% \mspace{14mu} {of}\mspace{14mu} {TEA}} = {\left\{ {{MW}\mspace{14mu} {of}\mspace{14mu} {{TEA}/{Repeat}}\mspace{14mu} {unit}\mspace{14mu} {MW}} \right\} \times 100}} \\{= {\left\{ {101.19/558.86} \right\} \times 100}} \\{= {18.1.}}\end{matrix}$

The boiling point of TEA is 88.8° C. Since the 20% wt loss is observedin the polymer only above 350° C., the polymer in the form of quaternaryammonium salt is very stable. This also implies that the structure ofpolymer remains intact at high temperatures.

Preparation of Polymer Solution in Water to Make Clear Coat

The quaternary ammonium salt of sulfonic acid group containing polymer(100 mg) of Example 1 was added to a sample bottle containing water (10mL). The sample was allowed to dissolve overnight.

A colourless solution was obtained. The pH of the solution was between 6and 7. A rectangular glass plate was covered with the polymer solutionby dropwise addition and the water was allowed to evaporate underambient conditions. After 18 h, the glass plate was covered with ahomogenous, transparent film which was free of cracks.

Adhesive to Bond Glass Plates

A rectangular glass plate was covered with the above mentioned aqueoussolution. Another glass plate of the same size was placed on top of theaqueous solution and the two slides separated by the layer of aqueoussolution were left in a fume hood overnight under ambient conditions.The glass plates were bonded together strongly and also showedbirefringence. Indeed, the birefringent nature was found to beconcentration dependent. Glass plates bonded together with a 1 wt %solution showed birefringence and those bonded together by a 5 wt %solution did not show birefringence. In both cases the adhesive layerwas transparent.

Preparation of Transparent Film

The quaternary ammonium salt of sulfonic acid group containing polymer(100 mg) of Example 1 was added to a sample bottle containing chloroform(1 mL). The polymer was allowed to dissolve completely and form a clearsolution. The top portion of a rectangular glass plate was then coveredwith this solution by dropwise addition and placed in a fume hood. After24 h, the glass plate was immersed in a 100 ml beaker containing 80 mLof hexane. A flexible, transparent, free standing, thin film wasseparated from the glass plate which was then dried under ambientconditions.

The flexibility of the film was tested by a simple manual bending testand it was found that the free standing film could be bent to 180°.

Equilibrium swelling ratio in 0.9 wt % NaCl solution=55% {Swellingratio=([Weight of swollen polymer−weight of dry polymer]/weight of drypolymer)×100}

The reversibility of swelling in deionized water is shown in FIG. 3. Foreach repetition, the polymer was allowed to reach equilibrium swellingand then dried at 80° C. for 24 hours. Ten repetitions were made. Noadverse change in swelling tendency was observed. This shows that thepolymer has a robust structure that can tolerate repeated swelling anddrying without loss of performance.

Example 2 Preparation of Quaternary Ammonium Salt of Sulfonic Acid GroupContaining Polymer Partly Grafted with Ethanol Amine

To an oven dried single neck round bottom flask, poly(maleicanhydride-altoctadecene) (3.5 g), and taurine (0.63 g) were added. Thesetwo solids were stirred slowly using a magnetic stirrer. DryN,N-dimethylformamide (DMF) (30 mL) was added through a syringe and thestirrer speed was increased. Triethylamine (0.5 g, 0.7 mL) was thenadded. The suspension turned light brown immediately after the additionof tertiary amine. The flask was then fitted with a double surfacecondenser and a drying tube on top of the condenser. This reactionmixture was heated slowly in an oil bath. At about 90° C., a clearsolution was obtained. Ethanol amine (0.31 g, 0.3 mL) was added andflask was heated to reflux for 18 h.

The reaction flask was then cooled and the DMF solution was addeddropwise to a beaker containing a large excess of water. The swollen gelwas separated by filtration, washed repeatedly with water. It was thentransferred to a beaker and dried.

Yield 4 g. Gel Permeation Chromatography (Polystyrene standard; THFeluent): Mn=17783; Mw=30194; Polydispersity=1.7.

IR (KBr) cm⁻¹: 3434, 2923, 1771, 1699, 1444, 1402, 1342, 1210, 1176,1041, 750.

¹H-NMR (CDCl₃) δ (ppm): 0.6-0.7 (t), 0.95-1.1 (b), 1.1-1.2 (t), 2.5-2.6(b), 2.85-3.0 (b), 3.3-3.65 (b), 9.2-9.5 (b). ¹³C-NMR (CDCl₃) δ (ppm):8.71, 14.13, 22.69, 27.72, 29.38, 29.77, 31.93, 35.57, 46.28, 59, 179.

Thermogravimetric analysis (TGA) (Nitrogen atmosphere; heating rate: 10°C./min): 5% weight loss at 298° C., 10% weight loss at 336° C. and 20%weight loss at 358° C.

Preparation of Water Based Gel

The polymer obtained in example 2 (0.5 g) was added to a sample bottlecontaining water (5 mL). The polymer was allowed to disperse in waterovernight. A stable, colourless, translucent gel was formed.

Example 3 Preparation of Quaternary Ammonium Salt of Sulfonic Acid GroupContaining Polymer Partly Grafted with Hexyl Amine

To an oven dried single neck round bottom flask, poly(maleicanhydride-altoctadecene) (3.5 g), and taurine (0.63 g) were added. Thesetwo solids were stirred slowly using a magnetic stirrer. DryN,N-dimethylformamide (DMF) (30 mL) was added through a syringe and thestirrer speed was increased. Triethylamine (0.5 g, 0.7 mL) was thenadded. The suspension turned light brown immediately after the additionof tertiary amine. The flask was then fitted with a double surfacecondenser and a drying tube on top of the condenser. This reactionmixture was heated slowly in an oil bath. At about 90° C., a clearsolution was obtained. Hexyl amine (0.51 g, 0.7 mL) was added and flaskwas heated to reflux for 18 h.

The reaction flask was then cooled and the DMF solution was addeddropwise to a beaker containing a large excess of water. The swollen gelwas separated by filtration, washed repeatedly with water. It was thentransferred to a beaker and dried.

Yield 3.6 g. Gel Permeation Chromatography (Polystyrene standard; THFeluent): Mn=12319; Mw=18649; Polydispersity=1.5.

IR (KBr) cm⁻¹: 3469, 2924, 2853, 1771, 1696, 1467, 1403, 1347, 1208,1177, 1041, 749.

¹H-NMR (CDCl₃) δ (ppm): 0.61-0.65 (t), 0.9-1.1 (b), 1.09-1.13 (t),2.5-2.6 (b), 2.912.94 (b), 3.15-3.25 (b), 3.7-3.8 (b), 9.7-9.8 (b).¹³C-NMR (CDCl₃) δ (ppm): 8.68, 14.02, 14.12, 22.54, 22.69, 26.58, 27.66,28.94, 29.15, 29.38, 29.5, 29.69, 29.77, 31.34, 31.93, 33.82, 35.53,46.2, 48, 179.

Thermogravimetric analysis (TGA) (Nitrogen atmosphere; heating rate: 10°C./min): 5% weight loss at 289° C., 10% weight loss at 337° C. and 20%weight loss at 363° C.

Preparation of Water Based Gel

The polymer obtained in example 3 (0.5 g) was added to a sample bottlecontaining water (5 mL). The polymer was allowed to disperse in waterovernight. A stable, colourless, milky white gel was formed.

Example 4 Preparation of Quaternary Ammonium Salt of Sulphonic AcidGroup Containing Polymer Partly Grafted with Hexyl Amine and EthanolAmine

To an oven dried single neck round bottom flask, poly(maleicanhydride-altoctadecene) (3.5 g), and taurine (0.63 g) were added. Thesetwo solids were stirred slowly using a magnetic stirrer. DryN,N-dimethylformamide (DMF) (30 mL) was added through a syringe and thestirrer speed was increased. Triethylamine (0.5 g, 0.7 mL) was thenadded. The suspension turned light brown immediately after the additionof tertiary amine. The flask was then fitted with a double surfacecondenser and a drying tube on top of the condenser. This reactionmixture was heated slowly in an oil bath. At about 90° C., a clearsolution was obtained. Hexyl amine (0.26 g, 0.3 mL) and ethanol amine(0.16 g, 0.16 mL) were added and flask was heated to reflux for 18 h.

The reaction flask was then cooled and the DMF solution was addeddropwise to a beaker containing a large excess of water. The swollen gelwas separated by filtration, washed repeatedly with water. It was thentransferred to a beaker and dried.

Yield 3.8 g. Gel Permeation Chromatography (Polystyrene standard; THFeluent): Mn=13392; Mw=21999; Polydispersity=1.6.

IR (KBr) cm⁻¹: 3445, 2923, 2854, 1771, 1698, 1467, 1403, 1346, 1177,1042, 750.

¹H-NMR (CDCl₃) δ (ppm): 0.86-0.9 (t), 1.2-1.3 (b), 1.34-1.38 (t),2.6-2.9 (b), 3.1-3.3 (b), 3.5-3.9 (b), 9.9-10.1 (b). ¹³C-NMR (CDCl₃) δ(ppm): 8.66, 14.02, 14.13, 22.52, 22.7, 26.58, 27.59, 28.94, 29.15,29.39, 29.51, 29.7, 29.77, 31.33, 31.94, 33.82, 35.54, 46.16.

Thermogravimetric analysis (TGA) (Nitrogen atmosphere; heating rate: 10°C./min): 5% weight loss at 293° C., 10% weight loss at 339° C. and 20%weight loss at 361° C.

Preparation of Water Based Gel

The polymer obtained in example 4 (0.5 g) was added to a sample bottlecontaining water (5 mL). The polymer was allowed to disperse in waterovernight. A stable, colourless, milky white gel was formed.

Example 5 Preparation of Quaternary Ammonium Salt of Sulfonic Acid GroupContaining Polymer Partly Crosslinked with Hexamethylene Diamine

To an oven dried single neck round bottom flask, poly(maleicanhydride-altoctadecene) (3.5 g), and taurine (0.63 g) were added. Thesetwo solids were stirred slowly using a magnetic stirrer. DryN,N-dimethylformamide (DMF) (30 mL) was added through a syringe and thestirrer speed was increased. Triethylamine (0.5 g, 0.7 mL) was thenadded. The suspension turned light brown immediately after the additionof tertiary amine. The flask was then fitted with a double surfacecondenser and a drying tube on top of the condenser. This reactionmixture was heated slowly in an oil bath. At about 90° C., a clearsolution was obtained. Hexamethylene diamine (0.23 g) was added and theflask was heated to reflux for 18 h.

The reaction flask was then cooled and the DMF solution was addeddropwise to a beaker containing a large excess of ethyl acetate andstirred well. The solid separated was allowed to settle. Theethylacetate layer was decanted off and the solid residue was washedrepeatedly with ethyl acetate. Then the beaker was air dried to constantweight.

Yield 3.8 g. Gel Permeation Chromatography (Polystyrene standard; THFeluent): Mn=18591; Mw=29166; Polydispersity=1.5.

IR (KBr) cm⁻¹: 3445, 2924, 2853, 1772, 1699, 1465, 1403, 1347, 1179,1041, 749.

¹H-NMR (CDCl₃) δ (ppm): 0.85-0.88 (t), 1.1-1.3 (b), 1.3-1.4 (t), 2.7-2.8(b), 3-3.1 (b), 3.1-3.3 (b), 3.6-3.8 (b), 9.65-9.8 (b). ¹³C-NMR (CDCl₃)δ (ppm): 8.72, 14.12, 22.69, 29.38, 29.76, 31.93, 34.02, 35.47, 46.28,179.4.

Thermogravimetric analysis (TGA) (Nitrogen atmosphere; heating rate: 10°C./min): 5% weight loss at 283° C., 10% weight loss at 330° C. and 20%weight loss at 360° C.

Preparation of Water Based Gel

The polymer obtained in example 5 (0.5 g) was added to a sample bottlecontaining water (5 mL). The polymer was allowed to disperse in waterovernight. A stable, colourless, translucent gel was formed.

Equilibrium swelling ratio in deionized water=357%

Equilibrium swelling ratio in 0.9 wt % NaCl solution=37%.

Example 6 Paint Composition

The polymer of Example 1 was added to a paint composition and thecontact angle of the exterior surface of the resulting paint composition(when dried) was measured (with water by a static method using agoniometer). The paint composition containing the polymer additive had acontact angle of 65.03°. A similar measurement made using an identicalpaint composition, except for the absence of the polymer, had a contactangle of 77°. Thus, the polymer lowered significantly the contact angle.Furthermore, the polymer was fully compatible with the paintcomposition, as indicated by the smoothness of the finished coating. Thepaint composition was an exterior wall coating made up of water basedemulsion containing latex and inorganic particles.

Comparative Example 1

Poly(maleic anhydride-alt-octadecene) (the starting material forExample 1) was dispersed in aqueous alkali solution at 10 wt %concentration and cast onto a glass plate. A similar test was done usingpoly(maleic an hydride-alt-octadecene) with chloroform as solvent. Inboth cases no film formation was observed.

Comparative Example 2

An alkali salt of poly(maleic anhydride-alt-octadecene), which is thestarting material for example 1, was prepared and added to water. Theresultant solution was opaque and inhomogeneous with the visiblesettling down of polymer.

Comparative Example 3

Poly(vinyl alcohol) was added to water. The resultant solution wasopaque and inhomogeneous with the visible settling down of swollenpolymer.

Comparative Example 4

Poly(vinyl alcohol) was added to water. The resultant solution wasapplied to a rectangular glass slide. Another glass plate of the samesize was placed on top of the layer of aqueous solution and left in afume hood overnight under ambient conditions. The glass plates werebonded together in a non-transparent manner and dispersed particles wereobserved throughout the bonded surface indicating the formation ofinhomogeneous adhesive layer.

To further illustrate certain aspects of the invention, the followingembodiments are disclosed with particularity:

1. A polymer having repeating units comprising a cyclic imido sulfonicacid according to formula I

wherein X and Y are selected to form an optionally substituted cyclicimido; and R_(S) is a sulfonic acid-containing group or salt thereof.2. A polymer according to embodiment 1, wherein the cyclic imidosulfonic acid according to formula I is the reaction product of apoly(cyclic anhydride) and an amino sulfonic acid.3. A polymer according to embodiment 2, wherein the cyclic anhydride isselected from alicyclic and aromatic anhydrides.4. A polymer according to embodiment 3, wherein the cyclic anhydride ismaleic anhydride.5. A polymer according to any one of embodiments 2 to 4, wherein theamino sulfonic acid is NH₂—R₁—SO₃H, wherein R₁ is selected fromoptionally substituted C₁ to C₁₀ alkylene and C₅ to C₂₀ arylene.6. A polymer according to embodiment 5, wherein the amino sulfonic acidis selected from taurine (2-aminoethanesulfonic acid) and metanilic acid(3-aminobenzenesulfonic acid).7. A polymer according to any one of the preceding embodiments, whereinR_(S) is a sulfonic acid salt and the salt is selected from a quaternaryammonium salt and an alkali metal salt.8. A polymer according to any one of the preceding embodiments, whereinin addition to the units comprising imido sulfonic acid groups accordingto formula I, the polymer comprises units derived from at least oneethylenically unsaturated monomer.9. A polymer according to embodiment 8, wherein each of the at least oneethylenically unsaturated monomer is selected independently from alkene(preferably ethylene, propylene, octadecene), styrene, vinyl pyrrolidineand (meth)acrylate(s) (preferably methyl methacrylate), isobutene, vinylpyridine, acrylonitrile, vinyl chloride and acrylic acid.10. A polymer according to any one of the preceding embodiments, whereinthe polymer comprises(1) 50 to 100% units according to formula II

wherein R₁ is selected from optionally substituted C₁ to C₁₀ alkyleneand C₅ to C₂₀ arylene, or a salt thereof; and(2) 0 to 50% units derived from at least one ethylenically unsaturatedmonomer.11. A polymer according to embodiment 10, comprising units according toformula III

whereinR₁ is selected from optionally substituted C₁ to C₁₀ alkylene and C₅ toC₂₀ arylene;each R₂ is selected independently from H and optionally substituted C₁to C₁₀ alkyl; andR₃ and R₄ are selected independently from H and optionally substitutedC₁ to C₃₀ alkyl, C₅ to C₂₀ aryl, pyrrolidinyl, carboxy and ester.12. A polymer according to embodiment 11, wherein R₃ and R₄ are selectedindependently from H and optionally substituted C₁ to C₂₀ alkyl13. A polymer according to embodiment 12, wherein R₃ and R₄ are selectedindependently from H and optionally substituted C₁₀ to C₂₀ alkyl14. A polymer according to embodiment 13, wherein R₃ and R₄ are selectedindependently from H and optionally substituted C₁₅ to C₁₈ alkyl.15. A polymer according to embodiment 14, wherein R₃ and R₄ are selectedindependently from H and optionally substituted C₁₅ to C₁₈ alkyl.16. A polymer according to embodiment 16, wherein R₃ is H and R₄ ishexadecyl.17. A polymer according to any one of embodiments 11 to 16, wherein R₁is selected from optionally substituted C₁ to C₆ alkylene and C₅ to C₁₅arylene.18. A polymer according to embodiment 17, wherein R₁ is selected fromoptionally substituted C₁ to C₄ alkylene and C₅ to C₁₀ arylene.19. A polymer according to embodiment 18, wherein R₁ is selected fromoptionally substituted C₂ to C₄ alkylene and C₅ to C₈ arylene.20. A polymer according to embodiment 19, wherein R₁ is selected fromethylene and phenylene.21. A polymer according to any one of embodiments 11 to 20, wherein eachR₂ is selected independently from H and optionally substituted C₁ to C₁₀alkyl.22. A polymer according to embodiment 21, wherein each R₂ is selectedindependently from H and optionally substituted C₁ to C₆ alkyl.23. A polymer according to embodiment 22, wherein each R₂ is selectedindependently from H and optionally substituted C₁ to C₃ alkyl.24. A polymer according to embodiment 23, wherein each R₂ is selectedindependently from H and ethyl.25. A polymer according to embodiment 24, wherein each R₂ is ethyl.26. A polymer according to any one of embodiments 11 to 25, wherein inaddition to units according to formula III, the polymer also comprisesunits according to formula IV

wherein R₅ is selected from optionally substituted C₁ to C₁₀ alkyl andC₅ to C₂₀ aryl; andR₃ and R₄ are as defined in any one of embodiments 2 to 16.27. A polymer according to embodiment 26, wherein R₅ is selected fromoptionally substituted C₂ to C₈ alkyl.28. A polymer according to embodiment 27, wherein R₅ is selected fromamine and hydroxyl substituted C₂ to C₈ alkyl.29. A polymer according to embodiment 28, wherein R₅ is C₆ alkyl.30. A polymer according to embodiment 29, wherein R₅ is selected fromhexyl and hexamethylamine.31. A polymer according to embodiment 30, wherein R₅ is optionallysubstituted C₂ alkyl.32. A polymer according to embodiment 31, wherein R₅ is ethylalcohol.33. A polymer according to embodiment 26, wherein R₅ is selected fromhexyl, hexamethylamine and ethylalcohol.34. A polymer according to any one of embodiments 11 to 33, wherein thepolymer comprises units according to formulae III, IV and V

whereinR₁ is as defined in any one of the preceding embodiments;each R₃ and R₄ is independently as defined in any one of the precedingembodiments; andR₅ and R₆ are selected independently from the definitions of R₅ in anyone of embodiments 26 to 33.35. A polymer according to embodiment 34, wherein R₅ and R₆ aredifferent.36. A polymer according to embodiment 34 or embodiment 35, wherein theunits according to formula III are present, as a % of all of the units,in an amount of at least 50%.37. A polymer according to any one of embodiments 34 to 36, wherein theratio of units of formula III to the total number of units of formulaeIV and V is at least 1.38. A polymer according to embodiment 37, wherein the ratio is at least5.39. A polymer according to embodiment 38, wherein the ratio is at least10.40. A polymer according to any one of embodiments 34 to 39, wherein thepolymer consists essentially of units according to formulae III, IV andV.41. A polymer according to any one of the preceding embodiments, whereinthe polymer is crosslinked.42. A polymer according to embodiment 41, wherein the polymer comprisescrosslinking groups according to formula VI

wherein R₇ is selected from optionally substituted C₁ to C₁₀ alkyleneand C₅ to C₂₀ arylene.43. A polymer according to embodiment 41 or embodiment 42, wherein thedegree of crosslinking is no more than 50%.44. A polymer according to any one of the preceding embodiments, whereinthe molecular weight of the polymer is in the range of 1000 to1,000,000.45. A polymer according to embodiment 44, wherein the molecular weightof the polymer is in the range of 5000 to 50,000.46. A polymer according to embodiment 45, wherein the molecular weightof the polymer is in the range of 10,000 to 50,000.47. A method of forming a polymer comprising the step of:

(1) reacting a poly(cyclic anhydride) with an amino sulfonic acid toform poly(imido sulfonic acid).

48. A method according to embodiment 47, wherein the poly(cyclicanhydride) is a co-polymer comprising units derived from (i) maleicanhydride and (ii) at least one ethylenically unsaturated monomer.49. A method according to embodiment 48, wherein the co-polymer isselected from poly(maleic anhydride-alt-octadecene), poly(maleicanhydride-alt-α-olefin), poly(maleic anhydride-alt-1-tetradecene) andpoly(maleic an hydride-alt-isobutene).50. A method according to any one of embodiments 47 to 49, wherein theamino sulfonic acid is used in a sub-stoichiometric amount such that notall of the cyclic anhydride is converted to an imido sulfonic acid instep (1), and the method includes the step of (2) reacting thepoly(cyclic anhydride) with a primary amine.51. A method according to any one of embodiments 47 to 50, wherein themethod includes the step of adding a tertiary amine to the reactionproduct of step (1) or step (2) to form a quaternary ammonium salt52. A method according to any one of embodiments 47 to 51, wherein thereaction temperature of step (1) is in the range of room temperature to200° C.53. A method according to embodiment 52, wherein the reactiontemperature of step (1) is in the range 60° to 180° C.54. A method according to any one of embodiments 47 to 53, wherein thereaction occurs in a dipolar aprotic solvent.55. A method according to any one of embodiments 47 to 54, wherein thereaction occurs in a high boiling point polar solvent.56. A method according to embodiment 54 or embodiment 55, wherein thesolvent is selected from N,N-dimethyl formamide, N,N-dimethyl acetamideand N-methylpyrrolidone.57. A polymer formed by the method of any one of embodiments 47 to 56.58. A latex comprising a polymer according to any one of embodiments 1to 46 and 57.59. A paint composition comprising a polymer according to any one ofembodiments 1 to 46 and 57.60. An adhesive comprising a polymer according to any one of embodiments1 to 46 and 57.61. A surfactant composition comprising a polymer according to any oneof embodiments 1 to 46 and 57.62. A surfactant composition according to embodiment 61, wherein thesurfactant is a liquid.63. A surfactant composition according to embodiment 61, wherein thesurfactant is a solid.64. A method of making a polymer latex, the method comprising the stepof dispersing the polymer of any one of embodiments 1 to 46 and 57 inwater.65. A method of preparing a paint composition, the method comprising thestep of mixing the polymer of any one of embodiments 1 to 46 and 57 withwater.66. A method according to any one of embodiments 1 to 46 and 57, whereinthe method includes the step of adding a pigment.67. A method of preparing an adhesive, the method comprising the step ofadding the polymer of any one of embodiments 1 to 46 and 57 to water.68. A method of preparing a surfactant composition, the methodcomprising the step of adding a polymer according to any one ofembodiments 1 to 46 and 57 to the composition.69. Use of a polymer according to any one of embodiments 1 to 46 and 57in a latex.70. Use of a polymer according to any one of embodiments 1 to 46 and 57in a paint composition.71. Use of a polymer according to any one of embodiments 1 to 46 and 57in a surfactant composition.

While the invention has been illustrated and described in detail in thedrawings and foregoing description, the same are to be considered asillustrative and not restrictive in character, it being understood thatonly the certain preferred embodiments have been shown and described,and that all changes and modifications that come within the spirit ofthe invention are desired to be protected.

1. A polymer having repeating units comprising a cyclic imido sulfonicacid salt according to formula I

wherein X and Y are selected to form an optionally substituted cyclicimido; and R_(S) is a quaternary ammonium salt of a sulfonicacid-containing group.
 2. A polymer according to claim 1, wherein thecyclic imido sulfonic acid salt according to formula I is the reactionproduct of a poly(cyclic anhydride) and an amino sulfonic acid.
 3. Apolymer according to claim 2, wherein the cyclic anhydride is selectedfrom alicyclic and aromatic anhydrides.
 4. A polymer according to claim3, wherein the cyclic anhydride is maleic anhydride.
 5. A polymeraccording to claim 2, wherein the amino sulfonic acid is NH₂—R₁—SO₃H,wherein R₁ is selected from optionally substituted C₁ to C₁₀ alkyleneand C₅ to C₂₀ arylene.
 6. A polymer according to claim 5, wherein theamino sulfonic acid is selected from taurine (2-aminoethanesulfonicacid) and metanilic acid (3-aminobenzenesulfonic acid).
 7. A polymeraccording to claim 1, wherein in addition to the units comprising imidosulfonic acid salt groups according to formula I, the polymer comprisesunits derived from at least one ethylenically unsaturated monomer.
 8. Apolymer according to claim 7, wherein each of the at least oneethylenically unsaturated monomer is selected independently from alkene(preferably ethylene, propylene, octadecene), styrene, vinyl pyrrolidineand (meth)acrylate(s) (preferably methyl methacrylate), isobutene, vinylpyridine, acrylonitrile, vinyl chloride and acrylic acid.
 9. A polymeraccording to claim 1, wherein the polymer comprises (1) 50 to 100% unitsof a quaternary ammonium salt of formula II

wherein R₁ is selected from optionally substituted C₁ to C₁₀ alkyleneand C₅ to C₂₀ arylene; and (2) 0 to 50% units derived from at least oneethylenically unsaturated monomer.
 10. A polymer according to claim 9,comprising units according to formula III

wherein R₁ is selected from optionally substituted C₁ to C₁₀ alkyleneand C₅ to C₂₀ arylene; each R₂ is selected independently from optionallysubstituted C₁ to C₁₀ alkyl; and R₃ and R₄ are selected independentlyfrom H and optionally substituted C₁ to C₃₀ alkyl, C₅ to C₂₀ aryl,pyrrolidinyl, carboxy and ester.
 11. A polymer according to claim 10,wherein R₃ and R₄ are selected independently from H and optionallysubstituted C₁₅ to C₁₈ alkyl.
 12. A polymer according to claim 10,wherein R₁ is selected from optionally substituted C₂ to C₄ alkylene andC₅ to C₈ arylene.
 13. A polymer according to claim 10, wherein each R₂is selected independently from H and optionally substituted C₁ to C₃alkyl.
 14. A polymer according to claim 10, wherein in addition to unitsaccording to formula III, the polymer also comprises units according toformula IV

wherein R₅ is selected from optionally substituted C₁ to C₁₀ alkyl andC₅ to C₂₀ aryl; and R₃ and R₄ are as defined in claim
 10. 15. A polymeraccording to claim 14, wherein R₅ is selected from amine and hydroxylsubstituted C₂ to C₈ alkyl.
 16. A polymer according to claim 15, whereinR₅ is selected from hexyl, hexamethylamine and ethylalcohol.
 17. Apolymer according to claim 10, wherein the polymer comprises unitsaccording to formulae III, IV and V

wherein R₁ is as defined in claim 10; each R₃ and R₄ is independently asdefined in claim 10; and R₅ and R₆ are selected independently from thedefinitions of R₅ in claim
 14. 18. A polymer according to claim 17,wherein R₅ and R₆ are different.
 19. A polymer according to claim 17,wherein the units according to formula III are present, as a % of all ofthe units, in an amount of at least 50%.
 20. A polymer according toclaim 17, wherein the ratio of units of formula III to the total numberof units of formulae IV and V is at least
 5. 21. A polymer according toclaim 17, wherein the polymer consists essentially of units according toformulae III, IV and V.
 22. A polymer according to claim 1, wherein thepolymer is crosslinked.
 23. A polymer according to claim 22, wherein thepolymer comprises crosslinking groups according to formula VI

wherein R₇ is selected from optionally substituted C₁ to C₁₀ alkyleneand C₅ to C₂₀ arylene.
 24. A polymer according to claim 22, wherein thedegree of crosslinking is no more than 50%.
 25. A polymer according toclaim 1, wherein the molecular weight of the polymer is in the range of10,000 to 50,000.
 26. A method of forming a polymer comprising the stepof: (1) reacting a poly(cyclic anhydride) with an amino sulfonic acid toform poly(imido sulfonic acid), and further including the step of addinga tertiary amine to the reaction to form a quaternary ammonium salt. 27.A method according to claim 26, wherein the poly(cyclic anhydride) is aco-polymer comprising units derived from (i) maleic anhydride and (ii)at least one ethylenically unsaturated monomer.
 28. A method accordingto claim 27, wherein the co-polymer is selected from poly(maleicanhydride-alt-octadecene), poly(maleic anhydride-alt-α-olefin),poly(maleic anhydride-alt-1-tetradecene) and poly(maleicanhydride-alt-isobutene).
 29. A method according to claim 26, whereinthe amino sulfonic acid is used in a sub-stoichiometric amount such thatnot all of the cyclic anhydride is converted to an imido sulfonic acidin step (1), and the method includes the step of (2) reacting thepoly(cyclic anhydride) with a primary amine.
 30. A method according toclaim 26, wherein the tertiary amine is added to the reaction product ofstep (1) or step (2) to form the quaternary ammonium salt.
 31. A methodaccording to claim 26, wherein the reaction temperature of step (1) isin the range 60° to 180° C. and wherein the reaction occurs in a dipolaraprotic solvent.
 32. A method according to claim 31, wherein the solventis selected from N,N-dimethyl formamide, N,N-dimethyl acetamide andN-methylpyrrolidone.
 33. A polymer formed by the method of claim
 26. 34.A latex comprising a polymer according to claim
 1. 35. A paintcomposition comprising a polymer according to claim
 1. 36. An adhesivecomprising a polymer according to claim
 1. 37. A surfactant compositioncomprising a polymer according to claim 1.